CA2075035A1 - Block copolymers from ionic catalysts - Google Patents

Abstract

A process for the production of block copolymers of ethylene and an .alpha.-olefin such as propylene by using an ionic catalyst system including a metallocene component and a component having a cation capable of donating a proton and a compatible non-coordinating anion. Novel block copolymers are produced.

Description

WO ~ 2S5 PClr/U~i91/008~5 l ' ~

~PEÇIFICATION

Cros$-Reference to Related Applications 1 This appli~ation is a Continuation-in-Part ~f U.S. P~tent 2 Application No. 477,791 filed February 9, 1990. U.S Patent Appllcation 3 No. 477,791 is in turn a Continuation in-Part of copending U.S. Patent 4 Application Nos. 133,052 filed December 21, 1987 and 133,480 filed December 22, 1987. Copending U.S. Patent Application No. 133,052 is in 6 turn a Continuation-in-Part of U.S. Patent Application No. 011,471 filed 7 January 30, 1987. Copending U.S. Patent Application No. 133,480 is in 8 turn a Continuation-in-Part of U.S. Patent Applioation No. 008,80~ f;led 9 January 39, 1987.

FIELD QF TS~E INV~NTION
lQ ~his ~nvention rel~tes to a method for preparlng bloc~ and t. tapsred copolymers by polymerlz'ng ethylene and other oleflns ln the presence of a catalyst ~hlch ~s a reactlon product of a metall~cene 3 component ~lth second component ~hlch co~pr~s~s a tatlon capable of 4 donatlng a proton and a compat~ble non-toord~natlng anion. More partlcularty, thls ~nventlon relates to a process for the productlon 6 of mutlblock and tapered copolymers of ethylenleally unsaturated 7 monomers. The lnvent'on llso related to the multlblock and tapered t~ 8 copolymers produ~ed.

BACKGROUHD OF THE INVENTION
81Ock copolymers are ~ell kno~n. They have been used co~mercla1ly as tomponents ln adheslYes, as melt processable rubbers, ... .. . . . . .
- , - , , -- -~, ...... :. - ~ :
. ,. . - ... ;; , : . . .

WO 91/1~28~ PCI'/US91/00835 , "
t, Z~`J~35 ' ~mpact reslstant thermoplastlcs, and as compatlblllzers, or 2 surfactants~, ~or emulslfylng polymer--polymer blends.
3 There has been wldespread lnterest ln polymer blends and 4 alloys. UnfortunatelY, most homopolymer palrs are lmmlsc1ble ~lth one another and give r~se to low strength rnaterlals due to the lack of 6 ~nterfaclal adheslon bet~een the separate phases. A block copolymer 7 is created ~hen t~o or more polymerlc segments, or blocks, of 8 different chemlcal composltlon are covalently bonded ln an end-to-end fashion. Block copolymers have certaln advantages over blends.
Firstly, the segments are covalently bonded to each other, thereby 11 el~mlnatlng the 'nterface problem. Secondly, block copo1ymers can be 12 used to strengt~en blends of lmmisclble polymers by servlng as 13 emulslf~ers, ~hi~h encourage physlcal connect~ons bet~een the phase, 1~ and thus lmprove the lnterfaclal adhesion and load transferrlng capabll~ty of t~e components.
16 While a ~lde varlety of block copolymer archltectures are 17 possible, most block copolymers of lnterest lnvolve the covalent 18 bonding of hard plast~c segments ~h~ch are crystalline or glassy, to 19 elastomeric blocks forming thermoplastic elastomers. Other block copolymers, such as rubber-rubber, glass-glass, and glass-crystalllne 21 block copolymers are also poss~ble and may have commerc~al 22 ~mportance. T~o common types of block copolymer structures are the 23 d~block and triblock forms. Ho~ever, multlblock copolymers, ln ~hlch 24 more than three segments are bonded together, are also deslrable.
Tr1blotk and multlblock sopolymers have the un~que abll~ty of 26 behavlng as thermoplastlc elastomers, comb~ning thermoplast~clty vlth 27 rubber-llke behàvlor. The key requlrements for ach~evlng 28 thermoplastlc elastomerlc behavior 1s the ablllty to develop a 2~ t~o-phase physlcal net~ork. Such a system li composed of a mlnor 30 fract~on of hard block, havlng a glass transltlon temperature ~9) or 31 meltlng temperature (Tm) above roo~ temperature, and a ma~or fraction 32 of a soft block, havlng a Tg belo~ room temperature. The hard blocks 33 assoclate to forln small morpholog~cal doma~ns that serve as physltal 34 crossllnklng and relnforcement s~tes. These states are thermally 35 reverslble makln!g 1t posslble to process the polymer as a melt at .. . . , : ..................... : :,., . ........ ".

., , , .,. . ,, - . , .: - . . - . .. . . :.:.

WO 91~1228~ P(~tUS91/00~3 2 ~7 l temperatures above the Tg or Tm of the hard block.
Block copolymers are slmllar to, yet dlst~nct from, tapered 3 polymers. In a tapered copolymer the compos~tlon of comonomer ls 4 gradually var~d from one end of the polymer to the other. Tapered copolymers are commerclally used a5 vlscosity modlfiers, oll 6 addlt~ves, ther~oplastlc elastomers, and lmpact-reslstant plastlcs.
7 Much ~ork has been done ln an attempt to syntheslze olefinic 8 block copolymers. The ldeal catalyst system ~ould produce a llvlng 9 polymer. Unllke typ~cal Zlegler-Natta polymerlzatlon processes l~v~ng polymerl~atlon processes ~nvolve only ln~t~at~on and ll propagat~on steps and are es5ent~ally devo~d of termlnatlng s1de 12 reactions. Thls permits the synthesls of the predetermined and 13 ~ell-controlled structures required for effective block 14 copolymerization. A polymer created ~n a ~llving system can have an - 15 extremely narro~ distr~but~on of molecular ~e~ght and be essent~ally16 monod~sperse. The li~ing polymer technlque ls unlquely sulted for the 17 preparation o~ block copolymers. Llvlng catalyst systems are 18 characterized by an ~nltlat~on rate ~hlth ~s conslderably hlgher than l9 the propagation rate, and the absence of terminatlon or transfer react~ons. In addition, these systems are character~zed by the 21 presence of a slng~e type of att~ve slte.
22 An~on~c polymerlzatlon routes to ~deal oleflnic block 23 copolymers have been much studled. Butadlene-~soprene block 24 copolymers have been synthes~ed us~ng the sequent~al addlt~on technlque. In sequentlal add~t~on, a ferta1n amount of one of the 26 monomers is contacted ~lth the catalyst. Onee the monomer has reacted 2~ to extlnct~on, formlng the f1rst block, a certa1n amount of the second 28 monomer spec~es 1s lntroduced and allo~ed to react to form the second 29 block. The process may be repeated as des~red us~ng the same or other 30 anlon~cally polymerlzable monomers.
31 Ethylene and other alpha-oleflns such as propylene and butene 32 are not dlrectly block polymerlzable by anlonlc technlques. Another 33 technlque ls descrtbed by Falk and Schlott 1n Macromolecules, 1971 4, 34 152. The flrst step ln the procedure lnvolves prepar1ng block 35 polymers contaln~ng polybutadlene and poly~soprene ~slng anionlc ,: , ~ ,~ ;;: ..... .
. .. ~ :

.. .. .. .. . .. . ..
-. , .~: , . ~-- : . . :, : ~. . .

5 PCI`/US91/01)835 ----~ ~Q~-S

' techn~ques. The lo~ pressure catalyt~c hydrogentatlon of the block 2 polymer obtalns the saturated block polymer.
3 The anlon~c routes to ~deal olef~nic block copolymers prov~de 4 a clean route to model block copolymers. Ho~ever the ~ethod ~s 1mpract~cal and ~5 not sufflclently versatlle for commerclal 6 purposes. For example the an~on1c route cannot be used to synthes ke 7 HDPE or isotact~c polypropylene (~-PP) segments.

8 A coordinatlon techn~que ~hlch has been used to syntheslze 9 block copolymers ~n~olves the use of vanadium catalysts at lo~
temperatures. Do1 et. al. ln ~acromolecul~ 1986 19 2896 sho~ed Il that a cata1yst prepared from 12 ~r1s(2-methyll-1 3-butaned~onato)vanad1um and Al(C2HS)2Cl ln 13 toluene has hlgh reactlv1ty ~n the l~v1ng coordlnatlon polymerlzatlon 14 of propene and that a ~ell-def'ned d'block copolymer of polypropylene and ethylene-propylene rubber can be prepared by adding ethylene 16 monomer durlng-the l~ving polymerizatlon of propene.
17 ~hile the Dol technique has the advantage over the anlonlc 18 routes of dispensing ~ith the hydrogenat'on step it does requ~re Yery 19 lo~ temperatures. The block copolymerizations carried out by Do~ et.
al. ~ere performed at -~0 and -60 C. Dol also reported ln ~.
21 Kaminsky and H. Sinn (Eds.) Trans't~on Hetals ~nd OrQanometalllcs as 22 Catalys~s ~Q~ Olefin Polvmer~zat~on Sprlnger-Verlag lg88 the llvlng 23 copolymer~2ation at -78 C of propylene ~th 1 5-hexadlene. An 24 addit~onal dlsadvanta~e of the technlque ls that lt cannot be used to produce 1-PP. turthermore. and no reports of the productlon of hlgh 26 dens~ty polyethylene (HDPE)~vla thls methoJ have appeared ln the 27 literature. ~he catalyst ttself ls poorl~ characteri ed and unstable.
28 Many cla1ms ln the prlor art have been made for the 29 product~on of block polymers ln the presence of 21egler-~atta type 30 catalysts. ~or example. ~P63-712 to ~ltsublshl Petrochemlcals cla~ms 31 a method of produc~ng a propylene block topolymer uslng a catalyst 32 1nclud~ng a solld t~tan1um component contalnlng ~agnes~u~ tltan1um 33 halogen and an electron-donor ~lth an organo-alumlnum cocatalyst to 34 prepare homopolypropylene ln a f1rst stage reactlon follo~lng ~hlch 35 1n a second stage of react~on bls(cyclopentadlenyl~ tltan1um ,. .

WO 91/1228~i PCI/US91/00835 2 ~s~ ?j~;

I d1chloride ts added and polymerlzat~on ~s cont~nued ln the presence of 2 added ethylene. The propylene block copolymers produced are said to 3 have high rigldity and lmpact strength and good mold~ng propertles.
4 U.S. Pa~ent 4,408,019 to Blunt relates to the use of a catalyst-actlvator system ~here'n t~tan~um ~s the sole metal component 6 to produce block copolymers of ethylene and propylene. The block 7 copolymers have the ~eneral formula ~AB)nA ~herein A 1s a 8 crystalline polypropylene block, each B 1s a randc~ ethylene-propylene 9 copolymer block, and n ~s an 1nteger from 1 to about 12. The I0 catalyst-activator ~s descrlbed as a combinatlon o~ titanium II tr1chlor1de as the catalyst and 12 d~methylb1s(methylcyclopentad1enyl)t1tanium as an actlvator. The 13 amount of ethylene 1n the block polymer ls typ'cally 40-65 ~t.X ~ith 14 5-15 ~t.~ present 1n the ~thylene-propylene segments. The I5 thermoplastlC block polymers are s~'d to have supetlor tensile 16 strength and lo~er compress~on set than prior art block polymers. In 17 d1scuss1ng pr10r art catalysts, Blunt observes that the productlon of 18 a true block polymer is dependent upon there being no permanent I9 interruption 1n the growth of any 91~en polymer cha1n unt11 all of the blocks have been completed. Moreover, Blunt states that the 21 traditional Ziegler-Natta catalysts based on t1tan1um halldes ~n 22 con~unction ~1th alkylalum~num compounds do not provlde a sufficlently 23 long cha1n 11fet1me to per~1t the format10n of block copolymers of 24 more than t~o copolymer blocks.
~hlle many patents and ~ubl1cat10ns cla1~ the synthesis of 26 block copolymers from ethylene and propylene, there 1s no ev1dence 27 tha~ these products ~ere obta~ned as ~ell defined biock polymers. The 28 kno~n k1netic features Qf heterogeneous ~ egler-Natta catalysts 29 suggest that it ls unlike1y that block polymers ~ere syntheslzed 1n 30 h~gh concentrat10ns- (J. Boor, ~1eqler-Natta Catalysts and 31 Polymer1zatlon$, Academ1c Press 1979). Accordlng to Boor, the 32 reported propylene and ethylene block copolymers are most 11kely 33 m~xtures of largely 1sotactlc polypropylene, polyethylene, and either 34 random, block, or tapered copolymers ~hkh are present ~n lo~
35 concentrat~ons, ~n the range of 0 to 20~.

.. . . . , . ~ . ... . . .. . ..
.. . . . . . . .-- ... . . .
.. - -, .... - . ..
. .. . . - .. - . . . ~ .

- : ~
- . ,.~

WO 91/1~285 PCr/US91/00835 2~ J~35 I As reasons for hls concluslon, Boor llsts a large number of 2 lnherent barrlers ~hlch must be overcome in uslng known Z~eg1er-Natta 3 catalysts to synthes ke block copolymersO For example, to syntheslze 4 ethylene/~-olef~ns blotk copolymers the follo~lng condltlons must be satlsfled: 1) all of the Tl centers must become actlve 6 s~multaneously; 2) all the Tl centers Inust stay allve durlng the 7 polymerkatlon; 3) all the Ti center; must have equal actlvlties for 8 polymer~zlng propylene and ethylene; 4) all the Tl centers ~ust be 9 equally access1ble to the ava'lable olefln molecules; 5) the -cross-over propagat~on rates must be hlgh for Tl-propylene centers to 11 be efflclently converted lnto Tl-polyethylene centers; 6) the centers 12 must be ~sotactlc-speclfic for propyl~ne polymerlzatlon and polymerlze 13 all ethylene molecules to a llnear polymer.
14 Several difficult~es arlse ln the use of known catalysts for IS the b)ock copolymerization of oleflns. Amor,9 those are the fact that 16 conYentlonal catalysts are typically multl-sited, and a slgn~flcant 1~ fractlon of the act~ve s~tes are unstable. Thls leads to rando~ chaln 18 ~nltlation and term~nation ~hlch, in turn, lowers the theoret~cal 19 block copolymer y~eld. ~hat ls des~red, and ~hat practlce of thls 1nvention provides, ~s a catalyst system ~lth ~ell-characterlzed 21 5tructure and reactivlty ~hich has a single act~ve slte. The system 22 should have Yell-def1ned and stable polymer~zat~on klnet~cs and be 23 free of aluminum alkyls or other chaln transfer agents.

SUMYARY OF ~HE IHVENTION
Z4 The lnventlon compr1ses a process for the productiQn of novel block copolymers of ethylene ~ith an a-olefin and the polymers ~6 obtained therefrom. The process lncludes sequentlally contact~ng 27 ethylene ~ith an ~-olef~n monomer in a suitable solvent at about O-C
28 in the presence of an ionlc catalyst to produce a block copolymer.
29 Thus, ~or example, ~hen a-PP-HDPE d~block is produced, the process provldes a diblock copolymer yield of 40-70X. The molecular ~e~ght of 31 the block copolymer may be cQntrolled by varying the 32 catalyst-to-monomer ratio. The lonlc catalyst ~hlch is a cr~tical 33 cc~ponent of the inventive polymerlzation process, compr~ses the . , . , . . ~
., : .
- , . . ". . - .

- . . ... .. , -WO 91/12~85 PCI'/US91/00835 z~ ~"J'Q3~

1 reaction product of a first component ~hlch ls a bis(cyclopentadienyl) 2 derivat~ve of a netal of Group IY-B of the Per~odic ~able of the 3 Elements, ~hich metal ~s capable of for~ng a cation formally having a 4 coordinatlon number of 3 and a valence of ~4; and at least one second component compr~slng a cat~on capable of donat~ng a proton and a ~ compat~ble non-coordinat~n9 an~on ~hich anlon is bulky and labile, and 7 capable of stabil~zing the Group IV-B metal cation ~lthout interfer~ng 8 ~ith the ability of sa~d ~roup IY-B metal cation, or ~ts decompositlon 9 product, to polymer~ze a-olefins to form tapered polymers and multlblock polymers such as di- and tr~-block homo-, and copolymers of 11 ethylene and propylene ~1th one or more other alpha-olefins.

DESCRIPTION QF THE PREFERRED EMBODIMENT~
12 The invention provides (1~ novel non-random di-, tri-, and 13 multi-block copolymers and tapered copolymers of ethylene, l-olefins, 14 diolefins, cyclic olefins, acetylenes and other unsaturated monomers;
and (2) the processes for polymerizlng sald non-random copolymers.

Ionlc Catalvst S~stem - General DescrlDtlon 16 The process of th~s lnvention is pract~ced ~lth that class of 1~ ~onic catalysts referred to, dlsclosed, and descr1bed 1n our copendlng 18 U.S. Patent ~pplkation Nos. 133,052 and 133,480. The ~onic catalyst 19 ~s prepared by combin~ng at least t~o components. The flrst of these ~s a bls(cyclopentadienyl) derlYatlve of a Group IV-B metal compound 21 containlng at least one 11gand ~hlch Ylll comb~ne ~ith the second 22 component or at least a port~on thereof such as a catlon portlon 23 thereof. Th~ second eomponent ls an ~on-exchange compound compr~sing 24 a cation ~h~ch ~111 lrrevers1bly react ~ith at least one llgand 25 contalned 1n sa~dl~roup IV-B metal compound and a noncoord~natin~
26 anlon ~hlch ls bulky, lab~le, and stab1e. Upon comblnatlon of the 27 flrst and second clDmponents~ the catlon of the second component reacts 28 ~lth one of the llgands of the flrst component, thereby generating an 29 ~on pa~r conslstlng of a Group IV-3 metal cation ~th a formal 3û coord~natlon number of 3 and a valence of ~4 and the aforement~oned 31 an~on, ~hlch anion ls compatlble ~th and non-coordinatlng towards the .. .. . . .... . . . . . . .
..... . . .. . .. . .. . .

- . .. . . .
r w o 91/l~28~ PCT/VS9~/OOg35 .

2~J~5 1 metal cation formed from the first component. The anion of the 2 second compound must be capable of stabilizing the Group IY-B
3 metal cation complex without interfering ~ith the Group IV-~ metal 4 cation's or its composition product's ability to function as a catalyst and must be sufficiently labile to permit displacement by 6 an olefin, diolefin or an acetylenically unsaturated monomer 7 during polymeri~ation.

A. The Metallocene ComPonent 8 The Group IV-B metal compounds; i.e., titanium, zirconium 9 and hafnium metallocene compounds, useful as first compounds in the preparation of the improved catalyst of this invention are 11 bis(cyclopentadienyl) derivatives of titanium, zirconium and 12 hafnium. In general, useful titanocene, zirconocenes and 13 hafnocenes may be represented by the following general formulae:
14 I. (A-Cp)MXlX2 2. (A-Cp)MX lX 2 16 3. (A-Cp)ML
17 4. (Cp*~(CpR) MXl 18 wherein ~Cp~ represents a c~clopentadienyl radical which may be 19 substituted or unsubstituted, and~
2Q (A-cp) is either ~Cp)(Cp*~ or Cp-A'-Cp* and Cp and Cp* are 21 the same or different cyclopentadienyl ring subst~tuted with 22 from zero to five substituent groups R.
23 The substituent groups R may be, independently, selected 24 from a wide variety of classes of radical groups which form covalent bonds to the carbon atoms of the Cp-rings. These 26 substituents act to modify the catalyst behavior by affecting the 27 symmetry, sterics, and electronics of the transition metal center.

, . . . ....... . . =.. = = . . .. .. . ..... _ . . .

, , - . , ........ , ., .... , .. : .: . . . .... . ... .. . .
.: .. . - . .. .. . - . . . . .~.

WO 91/122~5 PCI`/US91/00~35 ~ S

1 IllustratiYe but not limiting examples of suitable R substituents 2 include hydrocarbyl radicals containing from l to 50 carbon atoms;
3 substituted hydrocarbyl radicals wherein one or more of the 4 hydrogen atoms is replaced by a halogen radical, an amido raidca~
(XlX2N-), a phosphido radical ~XlX2P-), an alkoxy radical (XIO) or 6 any other radical containing Lewis acidic or basic functionality; .
7 hydrocarbyl substituted metalloid radicals ~here~n the metalloid 8 is selected from the Group IY-A of the Periodic Table of elements;
9 halogen radicals, amido radicals (XlX2N-), phosphido radicals (XlX2P-), alkoxy radicals (XlO~, alkylborido radicals (XlX2B-), or 11 any other radical containing Lewis acidic or basic functlonality;
12 or Cp and/or Cp* are a cyclopentadienyl ring in which two adjacent 13 R groups are joined forming a C4 to C20 ring to give a saturated 14 or unsaturated polycyclic cyclopentadienyl ligand such as indenyl, lS tetrahydroindenyl, fluorenyl, or octahydrofluorenyl; A' is a 1~ covalent bridging group between the two cyclopentadienyl groups; M
17 is titanium, zirconium or hafnium, L is an olefin, diolefin or 18 aryne ligant; Xl and X2 are, independently, selected from the 19 group consisting of hydride radicals, hydrocarbyl radicals having 20 from l to about 20 carbon atsms, hydrocarbyl radicals ~herein one 21 or more of ~he hydrogen atoms are replaced with a halogen atom, 22 organometalloid radicals comprls~ng ~ 6roup IY-A element wherein 23 each of the hydrocarbyl substitutions contained in the organic 24 portion of said organometalloid independently contain from l to 25 about 20 carbon atoms and the like; X'l and X'2 are joined and ..
26 bound to the metal atom to form a metallacycle, in which the metal 27 atom, X'land X'2 form a hydrocarbocyclic ring containing from 28 about 3 to about 20 carbon atoms; and R is a substituent, 29 preferably a hydrocarbyl substituent, on one of the cyclopentadienyl radicals which ls also bound to the metal atom.

WO 91/12~8~; PCl/US91/00835 2~ J~

1 Illustratlve, but not llmltlng examples of 2 bls(cyclopentad~enyl)Z'rCOn'Um compounds ~hlch may be used ln the 3 preparatlon of the lmproved catalyst of thls lnYentlon are 4 dihydrocarbyl-substltuted bls(cyclopentadlenyl~zlrconlum compounds such as bls(cyclopentadlenyl)21rconlllm dlmethyl, ~ bls(cyclopentadlenyl)zlrconlum dlethyl, bls(cyclopentadlenyl)zlrconlum 7 dlpropyl, bls(cyclopentadienyl)z~rconlum dlbutyl, bls(cyclopentadlenyl)zlrconlum d~phenyl, 9 bis(cyclopentadlenyl)zlrconlum dlneopentyl, bls(cyclopentadlenyl klrconium d~(m-tolyl), 11 bis kyclopentadlenyl)zlrcon'um di(p-tolyl) and the llke, 12 (monohydrocarbyl-subSt1tUted cyclopentadlenyl~21rconlum compounds such 13 as (methylcyclopentadlenyl)(cyclopentadlenyl) and 14 bls(methylcyclopentadlenyl)ZlrCOnlUm dlmethyl, ~ethylsyclopentadlenyl) (cyclopentadlenyl) and bls(ethylcyclopentadlenyl)zirconlum dlmethyl, 16 (propylcyclopentadienyl)(cyclopentadienyl) and 17 bis(propylcyclopentadienyl)zlrconlum dimethyl, 18 (n-butylcyclopentadlenyl) (cyclopentadlenyl) and 19 bis(n-butylcyclopentadlenyl)zlrconlum dimethyl, (t-butylcyclopentadlenyl) (cyclopentadlenyl) and 21 bls(t-butylcyclopentadlenyl)z'rcon'um dlmethyl, ?2 ~cyclohexylmethylcycloPentadlenYl) (cyclopentadlenyl~ and 23 b~s(cyclghexylmethylcyclopentadlenyl)zlrcon1um dlmethyl, 24 (benzy~cyclopentad~enyl~ (cyclopentadlenyl) and bls(benzylcyclopentadlQnYl)ZlrCon'um dimethyl, 2~ (diphenylmethylcyclopentadienYl) (~yclopentadlenyl) and 27 bls(dlphenylmethylcyclopentad'enyl)z~rcon'um d1methyl, 2~ (methylcyclopentadlenYl) (cyclopentadlenyl) and 29 blstmethylcyclopentadlenyl)Zlrconlum d~hydrlde, (ethy k yclopentadlenyl)(cyclopentadlenyl) and 31- b~s(ethylcyclopentad3enyl)Z'rcon~um dlhydrlde, 32 (propylcyclopentadlenyl)~cyclopentad~enyl) and 33 blstpropylcyclopentadlenyl)zlrconlum dlhydrlde, 34 (n-butylcyclopentadlenyl)(cyclopentadlenyl) and bls(n-butylcyclopentadlenyl)zlrconlum dlhydrlde, 36 (t-butylcyclopentadlenyl)~cyclopentadlenyl) and . . ., . .,. ; :. ,, , : . , WO ~1/122~5 PCI'/US91/00~3~

2~ 35 l bls~t-butylcyclopentadlenyl)21rconluln d~hydrlde, 2 (cyclohexylmethylcyclopentad'enyl)(cyclopentad'enyl) and 3 b~s(cyclohexylmethylcyclopentadlenyl)z~rcon~um d~hydr1de, 4 (benzylcyclopentad~enyl)(cyclopentadlenyl) and S b~s(benzylcyclopentadlenyl)~irconlum dlhydr~de, 6 (d~phenylmethylcyclopentadlenyl)(cycloPentadlenyl) and 7 b~s~diphenylmethylcyclopentadlenyl)Z~rCon~Um d~hydrlde and the llke;
8 lpolyhydrocarbyl-substituted-cyclopentad~enyl) 2l rconlum compounds 9 such as (dimethylcyclopentad~enyl) (cyclopentad~enyl) and lo b~s(dimethylcyclopentadlenyl) z~rconlum d~methyl, ll (trimetbylcyclopentad~enyl) (cyclopentad~enyl) and 12 bls(tr~methy7cyclopentad~enyl) zlrconlum d~methyl, 13 (tetramethylcyclopentadienyl) (cyclopentad~enyl~ and 16 bis(tetramethylcyclopentadlenyl) zlrcon1um dlmethyl, (permethylcyclopentad~enyl) (cyclopentad~enyl) and 16 b~s(permethylcyclopentadienyl) ~rconium dlmethyl, 17 (ethyltetramethylcyclopentad~enyl) (cyclopentad~enyl) and 18 bis(ethyltetramethylcyclopentadienyl) zirconlum dimethyl, 19 (~ndenyl)(cyclopentad~enyl) and bls(indenyl)zlrcon~um d~methyl, (dimethylcyclopentadlenyl) (cyclopentadlenyl) and 21 b~5(dimethylcyclopentadlenyl) z~rcon~um dlhydr1de, ~2 (trimethylcyclopentad~enyl) (cyclopentad~enyl) and 23 b~sltr~methylcyclopentad~enyl) zlrcon1um dlhydr~de, 24 (tetramethylcyclopentad1enyl) lcyclopentad~enyl) and bis(tetramethylcyclopentadienyl)z1rcon~um dlhydr1de, 76 (permethylcyclopentadlenyl~ (cyclopentadlenyl) and 27 b~s(permethylcyclopentad1enyl)z~rconlum dlhydrlde, 28 (ethyltetramethylcyclopentad~enyl) (cyclopentad~enyl) and 29 bis(ethyltetramethylcyclopentadienyl)z~rcon~um d~hydr~de, (~ndenyl)(cyclopentad~enyl) and b~s(~ndenyl)zlrconlum 31 (propylcyclopentad~enyl) (cyclopentadlenyl~ and 32 b~stpropylcyclopentad1enyl)z~rconlum d~hydr)de, .. -~ 33 ln-butylcyclopentad~enyl) (cyclopentad~enyl3 and 34 bls(n-butylcyclopentadlenyl)zlrconlum dlhydrlde, (t-butylcyclopentad1enyl) (cyclopentadleny7) and , .. . ., . .:

, ., . ", ~, .. .. .
. ~ , , -. , . ,:
. , w O 91/12~ cr/~s~/oo835 ( .:

~ 5 - 12 1 bis(t-butylcyclopentadlenyl)zlrconlum dlhydride, 2 ~cyclohexylmethylcyclopentadlenYl) (cyclopentadlenyl) and 3 b~s(cyclohexylmethylcyClopentad'enyl)2lrconlum d~hydrlde, 4 (benzylcyclopentad1enyl) (cyclopentaldlenyl) and b~s(benzylcyclopentadienyl)Z1rcon~um dihydr~de, 6 (d~phenylmethylcycloPentad'enYl) (cyclopentad~enyl) and 7 bls(diphenylmethylcyc'OPentad~enyl)~ircon1um dihydrlde and the llke;
8 (polyhydrocarbyl-subst'tuted-CY " Pentadieny') zlrconium compounds g such as (dlmethylcycloPentad~enYl) (cyclopentadienyl) and lo bis(dimethylcyclopentadienyl) 21rcon~um d~methyl, 11 (trimethylcyclopentadienyl) (cyclopentadlenyl) and 12 b~s(trimethylcyclopentadlenyl) z~rcon~um dimethyl, 13 (tetramethylcyclopentadienYl) (cyclopentadlenyl) and 14 bls(tetramethylcyclopentadienyl) zlrconlum di~ethyl, (permethylcyclopentadienyl~ ~cyclopentadienyl) and 16 bls(permethylcyclopentadlenyl) zirconium dlmethyl, 17 (ethyltetramethylCyclQpentad~enyl~ (cyclopentadienyl) and 18 bis(ethyltetramethylcyclopentadienyl)zirconium dlmethyl, lg (lndenyl)(cyclopentadienyl) and b1s(1ndenyl)zirconium dimethyl, (d~methylcyclopentad~enyl)(cyclopentadienyl) and 21 bis(dimethylcyclopentadienyl)zlrconSum dlhydride, 22 (tr~methylcyclopentadienyl) ~cyclopentad5enyl) and bls(tr~methylcyclopentadienyl) ~rcon~um dlhydr~de, 24 (tetramethylcyclopentad~enYl) (cyclopentadlenyl) and b~s(tetramethylcytlopentad1enYl )2~ rconiu~ d1hydr1de, 2~ (permethylcyclo~entadlenyl)(cYClOpentadlenyl) and 27 b~s(permethylcyclopentad~enyl)z~rcon~um d~hydrlde, 28 tèthyltetramethylcyclopentad~enyl)(cyclopentad~enyl) and 29 b~s(ethyltetramethylcyclopentad1enyl)z~rconlum dihydr~de, - 30 (1ndenyl)(cyctopentad~enyl) and bls(~ndenyl)~rconlum dihydride and 31 the llke; (metal hydrocarbyl-subst'tuted tyclopentadienyl)zirconium 32 compounds such as (trlmethyls~lylcyclopentadienyl)(cyclopentadienyl) 33 and bis(tr~methylsllylcyclopentad~enyl)z'rconium d~ethyl, 34 (tr~methylgermylcyclopentad~enyl)(cyclopentadienyl) and bis(tr~methylgermylcyclopentad1enyl)zircon~um d~methyl, :. ` ` . : , : ` , :: . . .,:; , ', .:,, , : .. : i . '' `-' ' , -W O 9~ 285 Pc~r/uS91tOO835 7 J~ 5 _ 13 -1 ~trlmethylstannylcycloPentadlenyl)(cyclopentadlenyl) and 2 b~s(trlmethylstannylCyclopentad~enyl)zlrconlum d~methyl, 3 (tr~methylplumbylCyclopentadlenyl)~cyclopentadlenyl) and 4 blsttrlmethylplumbylcyclopentad~enyl)z~rconlum dlmethyl, 5 (tr~methyls~lylcyclopentadlenyl)(cyclopentad1enyl) and 6 bls(tr~methyls~lylCyclopentad~enyl)z~rconlum d~hydrlde, ~ (trlmethylgermylcycloPentadienyl)(cyclopentadlenyl) and 8 b~s(trimethylgermylcyClopentad~enyl)2lrconlum dlhydrlde, g ~trlmethylstannylcYclopentadlenyl)(cyclopentadlenyl) and lo bls(trimethylstannYlcyclopentad~enyl)2irconlum dlhydrlde, : 11 (tr~methylplumbylcycloPentadienyl)(cyclopentad1enyl) and 12 bis(trlmethylplumbYlcyclopentad~enyl)z~rcon~u~ dlhydrlde and the l~ke;
13 (halogen-substltuted-cyclopentad~enyl) zlrconlum compounds such as 16 (trlfluoromethylcYclopentad~enyl)(cyclopentadlenyl) and b~s(trlfluoromethylCyClOPentad~enyl)zlrconlum dlmethyl 16 (trifluoromethylcycloPentadienyl)(cyclopentad1enyl) and 7 b~s(tr~fluoromethylfyclopentad~enyl~2ircon~um dihydrlde and the li~e;
18 silyl-subst~tuted b1s(cyclopentad~nyl) zircon~um compounds such as 19 bis(cyclopentad~enyl) (trlmethylsllyl)tmethyl)z~rEonlum, b~s(cyclopentadienYl) (triphenyls11yl)(methyl)zlrcon~um, 21 bis(cyclopentad~enYl) ~tr~s(dlmethyls~lyl)s~lyl~(methyl)zlrconium, 2~ b1s(cyclopentad~enyl)~b1s(meS'tYl)s~lyl~(methyl)71rconlum, 23 b1s(cyclopentad~enyl~(trlmethyls~lyl)ttl~ethyls1lylmet~yl) zirconium, 24 b1s(cyclopentad~enY') ~trlmethylsllylbenzyl) and the ll~e;
(bridged-cyclopentad~2nyl)zlrcon1um compounds such as methylene 26 b~s(cyclopentad1enyl)2~rconlum dlmethyl, 27 methylene(cyclopentad'enYl)21r onlum d~methyl, ethylene ...
: 28 bis(cyclopentad1enyl)2'rcon1um d'methyl, dimethylsllyl 29 b~s(cyclopentadlenYl)Z1rconlum dlhydrlde, ethylene 30 b~s(cycl~pentad~enyl)zlrcon'um dlhydrlde and d~methyls11yl ~ 31 b~s(cyclopentadlenYl)zlrcon~um dlhydr~de and the l~ke; chlral and - 32 C2-symmetlon compounds; ~zlrconacyclesn: assymetrically 33 brldged-dlcylopentadlenyl com~ounds such as 34 methylene(cyclopentadlenY~ fluorenyl)zlrcon1um dlmethyl, 35 d~methyslly(cycloPentadleny~ fluorenyl)zlrconlu~ dlhydrlde, .

., :, . . ` , . : . , -WO 91/1228; PCI/US91/00~35 j'' ~5 l àiphenylmethylene(cyclopentadienyl)(l-fluorenyl)~irconium dimethyl, 2 1sopropyl(cyclopentadienyl)(l-fluorenyl)~irconium dimethyl, 3 isopropyl(cyclopentadienyl)(l-octahydrofluorenyl)ZirCOnium dihydride, 4 dimethylsllyl(methylcyclopentadien~ l-fluorenyl)zirconium dihydride, methylene(cyclopent3d~enyl(tetramethylCyClOpentadienyl3z~rcon~um 6 dimethyl and the like: racemlc and meso 1somers of symmetrlcally 7 br1dged subst1tuted d1cyclopentadlenyl compounds such as 8 ethyleneb~(1ndenyl)zirconlum dlmethyl, 9 d1methylsilybis~1ndenyl~z1rcon~um d1methyl, ethyleneb1s(tetrahydro~ndenyl)z1rcon1u~ dlmethyl, ll d1methylsllyb1s(3-tr'methyls1lylcyclopentad~entyl)z1rcon1um d~hydr1de 12 and the l~ke; 2irconacycles such as bis(pentamethylcyclopentad1enyl) 13 z1rconacyclobutane, bis(pentamethylcyclopentad1eny~) 14 z~rconacyclopentane, bis(cyclopentadienyl)z~rconalndane, l-b~s(cyclopentadienyl)2~rcona-3-dimethyls'la-cyclobutane and the 16 11ke; olefin, diolefin and aryne llgand substituted 17 b1s(cyclopentadienyl)zircon~um compounds such as bis(cyclopentadienyl) 18 tl~3-butadiene)2irconium~ bis(cyclopentadienyl) l9 (2,3-dimethyl-1,3-butad1ene)z~rcon1um, bis(pentamethylcyclopentadienyl)(benzyne)zlrcon~um and the like;
21 (hydrocarbyl)~hydr1de) b1s(cyclopentadienyl)zirconium compounds sush 22 as b1s(pentamethylcyclopentad1enyl)21rcon1um ~phenyl)(hydr1de), 23 b1s(pentamethylcyclopentadlenyl)21rconium (methyl)(hydr1de) and the 24 llke; and bis~cyclopQntadlenyl) zlrconlum compounds ln whlch a substltuent on the cyclopentadlenyl radlcal ls bound to the metal such 26 as (pentamethylcyclopentadienyl) 27 (tetramethylcyclopentad~enylmethylene) z1rcon1um hydr1de, 28 tpentamethylcyclopentadienyl) 29 (tetramethylcyclopentad~enylmethylene)zirconlum phenyl and the 11ke.
A s1m11ar list o~ 11tustrat1v2 b1s(cyclopentad1enyl) hafnlum 31 and b1s(cyclopentadienyl)t1tan1um compounds could be made, but s1nce 32 the llsts ~lould be nearly ~dentlcal to that already presented ~1th 33 respect to b~s~cyclopentad~enyl)~1rconium compounds, such 11sts are :~ 34 not deemed essent1al to a complete d~sslosure. Other bls~cyclopentadienyl)hafnium compounds and other 36 b~s(cyclopentadleny))tltanium compounds as ~ell as other .
.. ,., ., , . .... ~ -. . -... . . .. - , . .. .
.: ... ; . ~ . .

~ : : . ..
.:. .. . . ,i : , .... . . ... . .

WO 9ltl~285 PCl/US91/0083~

; gl~JO~ 5 I b~s(cyclopentad~enyl)zlrconlum compounds ~h1ch are useful ln the 2 catalyst composltlons of thls lnventlon wlll of course be apparent 3 to those skllled ~n the art.

B. The A~ttvator Componen~

6 Compounds useful as an actlvator component ~n the preparat~on 7 of the catalyst of thls lnvention ~ll comprlse a cat10n ~h~ch ls a 8 Bronsted ac~d capable of donatlng a proton and a compat~ble 9 noncoordinat~ng anlon whlch anlon Is relatlvely large (bulky) capable I0 of stablllz~ng t~e actlve catalyst specles tthe Group IV-B cat10n) II ~hlch ~s formed ~hen~the two compounds are combined and sald an~on 12 ~ll be suff~c~ently labile to be d~splaced by olefln~c dlolefin~c 13 and acetylen~cally unsaturated substrates or other neutral Le~s bases 14 such as ethers nitriles and the like. In general suitable anions for I5 the second component may be any stable and bulky anionic complex having 16 the following molecular attributes: I) the anion should have a 17 molecular diameter greater than 4A; 2) the anion should form stable 18 ammonium salts; 3) the negative charge on the anion should be I9 delocali~ed over the framework of the anion or be local ked within the 20 core of the anion; 4) the anion should be a relatively poor 21 nucleophile; and 5) the anion should not be a powerful reducing or 22 oxidizing agent. Anions meeting these criteria - such as polynuclear 23 boranes carboranes metallacarboranes polyoxoanisns and anionic 24 coordination complexes are well described in the chemical literature.
25 Two classes of compatible non-coordinating anions meeting these criteria 26 haYe been disclosed in our copending US Patent Applications Nos. I33 052 27 and 133 480: I) anSonic coordination complexes comprising a plurality 28 of lipophilic radicals covalently coordinated to and shielding a central 29 charge-bearin~3 metal or ~etalloid core and 2) anions comprising a 30 plurality of boron atoms such as carboranes metallacarboranes and 3' boranes.
32 In general the act~vator compounds conta~n~ng slngle an10n1c 33 coord~nat~on complexes Yh~ch are useful ~n thls ~nvent10n ~ay be 34 represented by the follo~ng general formula:

[(L -H) ]dt(M ) Q~Q2---Qn' , , , , -;

, , .~ , , : ~ . . . ; , :...... . . .

wo 91/12285 PCI/US91/00~3S
i;

~ ~ ~ 5 - l6 -1 ~here~n:
2 L ls a neutral Le~1s base;
3 H ~s a hydrogen atom;
4 [L -H] ls a Bronsted acld;
M ls a metal or metallo~d selected from the Groups 6 subtended by Groups Y-B to V-A of the Per~odlc Table of the Elements;
7 ~.e., Groups Y-B, VI-B, VII-a, VIII, I-B, II-B, III-A, IV-A, lnd V-A;
8 Ql to Qn are selected, lndependently, from the 9 tlme, hydrocarbyl radlcals contaln~ng from l to about 20 carbon atoms, lO subst~tuted-hydrocarbyl rad~cals, ~here~n one or more of the hydrogen 1I atoms 1s replaced by a halogen atom, contalnln9 from l ts about 20 12 carbon atoms, hydrocarbyl-subst'tuted metal (organometalio~d) radl~als 13 ~here~n each hydrocarbyl subst~tut~on contalns from l to about 20 14 carbon atoms and said metal ~s selected from Group IV-A of the 15 Periodic Table of the Elements and the l~ke.

6 In general, Arl and Ar~ may, independently, be any 17 aromatic or substituted-aromatic hydrocarbon radical conta~ning from 18 about 6 to about 20 carbon atoms. Suitable aroma~lt radlcals lnclude, 19 but are not l~mlted to, phenyl, naphthyl and anthracenyl rad~cals.
2Q Su~table subst~tuents on the subst~tuted-aromat~c hydrocarbon 21 rad~cals, ~nclude, but are not necessar11y llmited to, hydrotarbyl 22 rad1cals, organometallo~d rad~cals, alkoxy rad~cals, alkylamldo 23 radicals, fluoro and fluorohydrocarbyl radlcals and the l~ke such as 24 those useful as X~ and X~. The subst~tuent ~ay be ortho, meta 25 or para, relag~ve to the carbon atoms bonded to the boron atom. When 26 either or both X~ and X4 are a hydrocarbyl radlcal, each may 27 be the same or ia different aromat~c or subst~tuted-aromatk rad~cal as 28 are Ar~ and Ar2, or the same may be a stralght or branched 29 alkyl, alkenyl or alkynyl radical having from l to about 20 carbon 30 atoms, a cycl~c hydrocarbon radical hav~ng fro~ about 5 to about 8 31 carbon atoms or an alkyl-subst~tuted cycl~c hydrocarbon rad~cal havlng 32 from about 6 to about 20 carbon atoms. X~ and X~ may also, 33 1ndependently, be alkoxy or dialkylam~do radlcals ~here~n the alkyl 34 port~on of sald alkoxy and d~alkylam~do radicals contaln fro~ l to 35 about 20 carbon atoms, hydrocarbyl rad~cals and organometallo~d 3~ radicals hav~ng from l to about 20 carbon atoms and the llke. As , . . ~

- ;, ~, ~ :. , .:-. . . ,.; ; ; ., . ~ . ,.
- : ;: : : : . :,:. : : .
, ~ : ~ . -.~. : ., . , :

WO 91/12285 P~/US91/0083~
r 2~7 I ~ndicated abo~e, Arl and Ar~ may be llnked to each other.
2 Slm~larly, elther or both of Ar~ an~ Ar2 could be llnked to 3 e~ther X, or X,. F~nally, X~ or X, may also be l~nked 4 to each other through a sultable br~clglng group.
Illustrat1~e, but not l~m~tlng, examples of boron compounds 6 ~h~ch may be used as an actlYator coMponent ln the preparat~on of the 7 1mproved catalysts of th's ~nventlon are tr~alkyl-substltuted ammonium 8 salts such as tr~ethylammon'um ~etra(phenyl)boron, tr~propylammonlum 9 tetra(phenyl)boron, tr~n-butyl)ammon'um tetra(phenyl)boron, trimethylammon1um tetra(p-tolyl)boron, trimethylammonlum 11 tetra(o-tolyl)boron. trlbutylammon~um tetra(pentafluorophenyl)boron, 12 tr~propylammon'um tetra(o,p-dlmethy'phenyl)boron, tr~butylammonlum 13 tetra(m~m-d1methylphenyl)boron~ trlbutylammon~um 14 tetra(p-tr~-fluoromethylphenyl)boron~ trl(n-butyl)ammonlum tetra(o-tolyl)boron and the llke; N,N-dlalkyl anllln~um salts such as 16 N,N-dimethylanilinium tetra(pentafluoro phenyl)boron, 17 N,N-diethylan~11n1um tetra(phenyl)boron, 18 N~N-2~4~6-pentamethylan'l~nlum tetra~phenyl)boron and the llke;
l9 d~alkyl ammonlum salts such as di(l-propyl)ammonlum tetra(pentafluorophenyl~boron~ dlcyclohexylammon~um tetra(phenyl)boron 2l and the l~ke; and trlaryl phosphon1um salts such as 22 tr~phenylphosphonlum tetra(phenyl)boron, trl(methylphenyl)phosphon~um 23 tetra(phenyl~boron. trl(dimethylphenyl)phosphon~um tetra(phenyl)boron ~4 and the l~ke.
S~mllar 11sts of sultable compounds contalnlng other metals 26 and metallo~ds ~h~ch are useful as act1vator components may be made, 27 but such 11sts are not deemed nécessary to a complete d~silosure. In 28 th~s regard, lt should be noted that the forego1ng 11st 1s not 29 1ntended to be exhaust1Ye and that other useful boron compounds as ~ell as useful compounds contalnlng othet metals or metallolds ~ould 31 be readlly apparent to those sk~lled ~n the art from the foregoing 32 general equat10ns.
33 Actlvator components based on anlons ~h~ch conta~n a 34 plural1ty of boron atoms may be represented by the follo~lng general formulae:

36 6. ~L ~ct(CX)a)(~ X )mX b]

. .
- - - . . ~ . . .. ... . .
. ; .: . . . . . . , , ~ , , .
, . , .; . . . . .. .
,; , .~
.. . , . .. ; . . . .
~; . ., . . . . . . . :

WO gl/1~85 P(:~/US91/00835 - 1~

1 7 [L ~H]d~['Cx3)a~(M~x4)ml(x5)~l~ ]2H J

2 ~herein ~L -H] ls elther H~, ammonium or a substltuted 3 ammonlum catlon having up to 3 hydro~en atoms replaced ~lth a 4 hydrocarbyl rad1cal contaln1ng from l to about 20 carbon atoms or a 5 substltuted-hydrocarbyl rad~cal, ~herein one or more of the hydrogen 6 atoms ls replaced by a halogen atom, contaln1ng from l to about 20 7 carbon atoms, phosphonlum rad~cals, subst~tuted-phosphonlum 8 radlcals haY~ng up to 3 hydrogen atoms replaced ~lth a hydrocarbyl 9 radlcal contalnlng from l to about 20 carbon atoms or a I0 substltuted-hydrocarbYl radlcal, where1n 1 or more o~ the hydrogen lI atoms 1s replaced by a halogen atom, conta1nlng from l to about 20 12 carbon aeoms and the 11ke; C ls carbon; M ls boron or phosphorus, 13 each of X, X , XU, Xa X, and-X~ are radlcals selecteJ, 14 1ndependently, from the group consistlng of hydrlde radlcals, hallde 15 radicals, hydrocarbyl radlcals conta~nlng from l to about 20 carbon 16 atoms, substituted-hydrocarbyl rad~cals, ~here~n one or more of the 17 hydrogen atoms 1s replaced by a halogen atom, contalnlng from l to 20 ~ carbon atoms, organometallo~d radicals ~herein each hydrocarbyl l9 substitution ~n the organo port1On contains from l to about 20 carbon 20 atoms and sa~d metal ~s selected from Group IV-A of the Periodlc 21 Table of the Elements and the like; M ~s a transltion metal; a and 22 ~b~ are ~ntegers > 0; c 1s an ~nteger > l; a ~ b ~ c ~ an 23 even-numbered 1nteger from 2 to about a; and ~m ls an lnteger r 24 rang1ng from 5 to about 22; la and ~b are the same or a different 25 1nteger ~ 0; ~c ~ 1s an 1nteger > 2; a ~ b ~ c ~ an 26 even-numbered 1nteger from 4 to about 8; a~ 5 an lnteger from 6 to 27 abouS 12; n~ 1s an lnteger such that 2c - n . d; and "d~ ls an 28 ~nteger greater than or equal to l.
: 29 Illustrat~ve, but not 11m1tlng, examples of second 30 components ~h1ch can be used ln preparing catalyst systems util~zed 31 in the process of this ~nvent1On ~here~n the an1On of the second 32 component conta1ns h plural1ty of metallo~d atoms (as 1n formulae S
33 and 6) are am~onlum salts such as ammonlum l-carbadodecaborate (uslng 34 l-carbadodecaborate as an lllustratlve, but not llmlting, counterion 35 for the ammonlum catlons llsted belo~): monohydrocarbyl-substituted 36 ammonlum salts such as methylammon1um l-carbadodecaborate, 37 ethylammon1um l-carbadodecaborate, propylammon1um ., . ................ . . -, . .

. ..: . . , , . : . , : . . " ., ., . , : . ~ :

WO 91/122~5 PCI/US91/00835 2~ 5 1 l-carbadodecaborate, lsopropylammonlurn l-carbadodecaborate, 2 (n-butyl)ammonlum l-carbadodecaborate, anltlnlum l-carbadodecaborate, 3 and (p-tolyl)ammonlum l-carbadodecaborate and the llke;
4 d~hydrocarbyl-subst1tuted ammonlum salts such as dlmethylammonlum S l-carbadoâecaborate, dlethylammon~um l-carbadodecabora~, 6 dlpropylammon~um l-carbadodecaborate, dl~sopropylammonlum 7 l-carbadodecaborate, dl~n-butyl) ammonlum l-carbadodecaborate, 8 d~phenylammon~um l-carbadodecaborate, d~(p-tolyl)ammonlum 9 l-sarbadodecaborate and the l~ke; tr~hydrocarbyl-subst~tuted ammonlum 13 sal~s such as trlmethylammon1um l-carbadodecaborate, tr~ethylammon1um 11 l-carbadodecaborate, tr1propyl-ammonium l-carbadodecaborate, 12 tr~(n-butyl) ammonlum l-carbadodecaborate, tr~phenylammon1um 13 ~-carbadodecaborate, trl(p-tolyl~ammon~um l-carbadodecaborate, 14 N,N-d~methylanlllnlum l-carbadodecaborate, N,N-dlethylanll1n~um 15 l-carbadodecaborate and the llke.
16 Illustratlve, but not l~mltlng examples of second compounds 17 correspondlng to Formula 5 tuslng trl(n-butyl)ammon~um as an 18 illustrative, but not llmitlng, counterlon for the an~ons listed 19 belo~l are salts of an~ons juch as b~sttr1~n-butyl)ammonlum~
20 nonaborate, b1sttr~n-butyl)ammon~um~decaborate, b1s~tri(n-butyl) 21 ammonium]undecaborate, b1sttr1(n-butyl)ammonium~ dodecaborate, ~2 bis[trl(n-butyl)ammon~um]decaChlorodecaborate. tr~(n-butyl)ammonium 23 dodecachlorododecaborate, tr~(n-butyl)ammonium l-tarbadecaborate, 24 tri(n-butyl) ammon~um l-carbaundecaborate, tr1(n-butyl)ammon~um 25 l-carbadodecaborate, tr~(n-butyl)ammon~um 26 l-tr~methylsllyl-l-carbadecaborate, tritn-butyl)ammon~um 27 dlbromo-l-carbadodecaborate and the llke; borane and carborane 28 complexes and salts of borane and carborane anlons such as 29 decaborane~l4), 7,8-d~carbaundecaborane(13~, 30 2,7-dkarbaundlecaborane(13), 31 undecahydrldo-7,8-d~methyl-7,8-d~carbaundecaborane, 32 dodecahydrldo-11-methyl-2,7-d1-carbaundecaborane, trl(n-butyl~
33 ammonlum undecaborate(l4), tr~n-butyl)ammonlum 34 6-carbadecaborate(12), trl(n-butyl)ammonlum 7-carbaundecaborate~13~, 35 tr~(n-butyl)ammonlum 7,8-dicarbaundecaborate(12), .. . . . ~ , . , .- : . l :
..

WO 91/1228~ PCI/US93/00835 , 2r~ 5~J~

1 trl(n-butyl)ammonlum 2,9-dlcarbaundecaborate(12), 2 trl(n-butyl)ammon1um dodecahydrldo-8-methyl-7,9-dlcarbaundecaborate, 3 trl(n-butyl)ammonlUm undecahydrldo-8-ethyl-7,9-dScarbaundecaborate, 4 trl(n-butyl) ammon~um undecahydr~do-lB-butyl-7,9-d1carbaundecaborate, 5 tri(n-butyl)ammonlum undecahydrldo-8-allyl-7~9-d~carbaundecaborate~
~ tr~(n-butyl~ammon~um 7 undecahydr~do-9-trlmethylsllyl-7,8-dlCarbaundecaborate, 8 tr~(n-butyl~ammonlum undecahydr~do-4,6-dlbromo-7-carbaundecaborate 9 and the l~ke; boranes and carboranes and salts of boranes an~

10 carboranes such as 4-carbanonaborane(14), 1~3-dlcarbanonaborane(l3)~

11 6,9-d~carbadecaborane(14).

12 dodecahydrldo-1-phenyl-1,3-dlcarbanonaborane, 13 dodecahydrldo-1-methyl-1,3-dlcarbanonaborane, 14 undecahydrldo-l~3-d'methyl-l~3-d'carbanonaborane and the ll~e.

15 Illustratlve. but not llmitlng, exa~ples of second compounds 16 corresponding to Formula 7 tusing trl(n-butyl)ammonlum as an 17 lllustratlve, but not llmlting, counterlon fot the anlons llsted 18 belo~ are salts of metallacarborane and metallaborane anions such as r 19 tri~n-butyl)ammonium bls(nonahydrido-1,3-dicarbanonaborato) 20 cobaltate(III), tr~(n-butyl)ammonlum 21 bls(undeca-hydrldo-7~B-d~carbaundecaboratoferrate(III)~ trl(n-butyl) 22 ammonlum blstundecahydrldo-7~8-dlcarbaundecaborato)cobaltate~III)~

23 tr~(n-butyl)ammonlum b~stundecahydrldo-7,8-dlcarbaunaborato) 24 n~kelate~III), trl(n-butyl~ammon1um bls(nonahydrldo-7, 25 a-dimethyl-7,8-d karbaundecaborato)~errate(III), trl~n-butyl)ammonlum 26 b~s~nonahydrldo-7~8-d'methyl-7~8-dlcarbaundecaborato~chromate(III)~

27 tri~n-butyl)ammonlum 28 bis~trlbromooctahydrido-7~8-dlcarbaundecaborato)cobaltate(III)~

29 tri(n-butyl)ammonlum b~s~dodecahydrldodlcarbadodecaborato) 30 cobaltate(llI), trlsttri(n-butyl)ammonium~ bls 31 ~undecahydr~do-7-carbaundecaborato)chromatetIII), ,. : , ; . ~ . ~

W;O 91/1228~ PCr/US91/00835 Z~

1 b~s[trl~n-butyl~ ammonlum~
2 bls(undecahydr1do-7-carbaundecaborato)manganate(IY), 3 b~sttrl(N-butyl)ammOnlum~ b~s(undecahydrldo-7-catbaundecaborato) 4 cobaltate(lII), bls~tr~ (n-butyl)ammonlum]
b~s(undecahydr~do-7-carbaUndecabOratG) nlckelate(IV) and the l~ke. A
6 s~m11ar l~st of representatlve phosphonlum compounds can be reclted 7 as lllustrati~e second compounds, but for the sake of brevlty, lt ls 8 s~mply noted that the phosphonlum and subst~tuted-phosphonlum salts 9 correspond~ng to the llsted ammonl w and subst~tuted-ammonlum salts 10 tould be used as second compounds ~n the present lnvefltlon~ `~

Cho~ce of Metallocene-Actlvator Palrs II In general, and ~h~le most metallocene components ~dentlf~ed 12 above may be comb~ned ~th most actlYator components ldentlfled above 13 to produce an actlve olef~n polymerlzat~on catalyst, lt ~s lmportant 14 for cont~nulty of the polymerl~at~on operat~ons that either the metal 15 cat~on in~ttal1y formed from the metallocene component or a 16 decomposition product thereof be a relati~ely stable catalyst. It ~s 17 also lmportant that the an~on of the act~vator compound be stable to 18 bydrolysls ~hen an ammonium salt ~s used. Further, 1t ~s important 19 that the ac~dity of the activator csmponent be suff~clent, relat~ve 20 to the metallocene component, to facllltate the needed pro~on 21 transfer. Act~vator compounds conta~ning aryl-a~monlum salts such as 22 N,N-dlmethylan~l~Um are more ac~d~c than tr~alkylammon~um salts and 23 there~ore are useful Yith a ~der Yarlety o~ metallocene components.
24 The bas~c~ty of the metal complex Yust also be suff1c~ent to 25 facllttate the needed proton transfer. In general, 26 b~s(cyclopentad~enyl)metal compounds ~h~ch can be hydrolyzed by 27 aqueous solut~ons can be cons1dered su~table as ~etallocene 28 components to form the catalysts descr1bed hereln.
29 The chem~cal reactlons ~hlch occur may be represented by 30 reference to the general formulae set forth here~n as follo~s:

.... . ..
. . - - : ; . . ....................................... -.- ~, ;. .
. - .. . ~ . .

WO 91/122X~ . PCr/US91/00835 ~. .
Z~7;-~35 I A. (A-Cp)MXlX2 ~ [L -H] [B ~ - [(A-Cp)MX~3 [B ~ ~ HX2~L or 2 [(A-Cp)MX2~tB ] ~Xl~L
3 B. (A-Cp)HX ~X -2 ~ tL -H] tB ] E(A-Cp)MX lX 2N~[B ~ ~L or 4 t(A-Cp)MX 2X lH~-tB ] ~L

C. (A-Cp)ML + ~l -H~ (A-Cp)M(LH)~tB ~ ~L

D. (Cp~)~RCp)MX~ ~ [L -H]~[B ~ t(Cp*)(HR-Cp)MX~ B ] ~ L or [(Cp~ -Cp)M]~tB ~ ~ HXi ~ L
7 In the foregolng react~on equatlclns the letters A-D
8 correspond to the numbers 1-4 respect~Yely set forth ln comb~nation 9 ~ith the general equdt~ons for useful metal~otene tompounds. B
10 represents a compatible ~on correspond~ng to the general formulae 11 outl~ned ~n formu!ae 5 S and 7 above. ~hen the metallocene and 12 act~vator components used to prepare the 1mproved catalysts of the 13 present lnvent~on are comb~ned ~n a su~table solvent or dlluent all 14 or a part of the catlon of the actl~ator ~the ac~d~c proton) comb~nes 15 ~lth one of the substltuents on the metallocene compound. In the case 16 ~here the metallocene component has a formula correspond~ng to that of 17 general formula 1 a neutral compound ~s l~berated ~hlch neutral 1~ compound e~ther remalns ln solut10n or ls l~berated as a gas. In this 19 regard ~t should be noted that lf e~ther X1 or X2 ln the 20 metallocene componen~ ls a hydrlde hydrogen gas may be llberated.
21 S~larly if elther X~ or Xa ls a methyl rad~calt methane may 22 be ~berated as a gas. In the cases ~here the flrst component has a 23 formula correspond~ng to those of general formulae 2 3 or 4 24 (opt~onal) one of thP substltuents on the metallocene component ls 25 protonated ~ut no substltuent ~s l~berated. In general the stab~l~ty 26 and rate of format~on of the products ln the foregoSng react~on 27 equat~ons ~111 vary dependlng upon the cholce of the solvent the 28 acldlty of the tL -H]~ selected the partlcular L the anlon the 29 temperature at ~hich the reactlon 1s completed and the partlcular 30 cyclopentadlenyl derlvatlve of the metal selected.
31 ~th respect to the comblnat~on of the metallocene component 32 ~th the act~vator component to form a catalyst of thls lnvent~on lt .. ...

, , : . ~ ::. . : . . :

WO 91/1228~; PCr/US91/00835 .

l should be noted that the t~o compounds comblned for preparatlon of the 2 active catalyst must be selected so as to avold transfer of a fragment 3 of the an~on to the meta) catlon, thereby formlng a catalytlcally 4 1nact~ve specles. Th~s could be done by sterlc h~ndrance, resultlng 5 from substitutions on the cyclopentad~enyl carbon atQms as ~ell as .
6 subst~tutions on the non-coordlnating an~on.
7 It follo~s, then, that the metallocene components compris~ng 8 perhydrocarbyl-subst~tuted cyclopentad~enyl radlcals could be r 9 effectiYely used ~ith a broader range of activator compounds than 10 could metallocene components compr~sing unsubst~tuted cyclopentadlenyl Il radlcals.
12 As the amount and size of the substitutions on the 13 cyclopentadienyl radicals are reduced, however, more effectlve 14 catalysts are obtained ~ith act~vator compounds conta~ning 15 non-coordinating anions which are larger in size and more resistant to 16 degradation. In the case ~here the non-coordinating anion ~s an 17 anlon~c coord~nat~on complex, such as a tetraphenylboron der~vatlve, l8 substltut~ons on the phenyl rings can be used to prevent the transfer l9 of a proton or an entire phenyl group from the an~on to the metal.
20 Th~s can be accomplished by alkyl substitutlon in the ortho pos~t1Ons 21 of the phenyl groups, or, more preferably, by perfluoro-subst~tutlons 22 on the anlon. Thus, an~onic coordinat~on complexes conta~ning 23 perfluorphenyl-, trlfluoromethylphenyl-, or b~s-trifluormethylphenyl 24 r~ngs are preferred for th~s subgenus of act~vator components. When 25 the non-coord~nat~ng anlon conta~ns a plural~ty of boron atoms as 26 descrlbed in general for~ulae 6 and 7, more effective catalysts are 27 obtained vith activator compounds contalning larger anions, such as 28 those encompassed by ~quat~on 7 and those hav~ng larger m Yalues ~n 29 Equat~on 6. In these cases it is further preferable hhen us~ng second 30 compounds ~h~ch are encompassed by Equation 6, that a I b ~ c D 2.
31 Second compounds in ~hlch a ~ b ~ c ~ even-numbered ~ntegers of 4 or 32 more have acidic ~-H-B mo~eties ~hich can react further ~ith the metal 33 cation formed, leading to catalytlcally ~nactive compounds.

34 As ind~cated supra, most metallocene compounds ~ill comblne - 35 ~th most activator compounds to give an active polymerizatlon .
. . , ,~
. ~
~ '~' ' ' I' ~ ' , Wo ~1/1228~ PCr/US91/00835 .

~? ~ ~ 3~ J5 - 24 -1 catalyst. The ln~t~ally formed catalyst ls not, ho~ever, always 2 sufflclently stable as to permlt 1ts separat10n and subsequent 3 ldent~f~catlon. Ho~ever, cataly5ts ~hlch are thermally stable are 4 preferred for the productlon of block or tapered copolymers. Three structurally dl5t~nct forms of thermllly stable lonlc catalysts have 6 been ldentified by NMR spectrosco~y and are sho~n below ln equation 8.

7 8a . tA-CpMXl ] t (C2B,H 1 l ) 8 Bb. tA-CpMX~(L )~[B(C~Fs),(X,)l 9 8c . t(A-Cpl~Kl)2Xl] [B ]

In the foregoing reactlons the symbols A-Cp, M, Xl, L and X~
ll correspond to the def~nitions set forth ln equations 1-4 and 5-~a, 12 respectlvely; B represents a compatible non-coordinatlng anlon 13 corresponding to the general formulae set forth ln equatlons 5, 6 and 14 7. In example 8a, NMR spectroscopy lndicates that ~he metallacarborane anlon ~s weakly bound to the metal center; the 16 biproduct L does not form an observable coordination complex ~lth the 17 metallocene center. In 8b, NMR experlments indlcate that the 18 fluorinated boron anion ls completely non-coordinating and that L , l9 ~eakly coordinates to and stabilizes the metallocene tatlon Yhen the -~
tertiary amine (L ) ls an anillne derivative. The abllity of L ~o - 21 coordinate to the metal 1s 1mportant to the stab~l1ty of the catalyst 22 systems ~hlch have hlghly noncoordlnat'ng anions. The Levls baslclty 23 of the L can affect the rate of potymerlzation and other 24 polymeri2ation parameters. Experlenc2 has sho~n that ~hen the bulk of the amine or the metallocene cat~on is 1ncreased by subst~tutlons on 26 the n~trogen atom or the cyclopentad~enyl llgands respectl~ely, the 27 abillty for the amlne to coordinate to the metal center Jecreases.
28 Add~t~on of excess metallocene A~pM(Xl~2 to 8a or 8b results 29 ~n d~splacement of the anlon ~n 8a or the anlllne llgand ln Bb to form a stable dlmerlc catlon 8c.

WO 91/1228~ PCr/US9lt01)835 ~f~ 5 1 Preferred Cat~lysts for ~he Productlpn of Block and TaDered .
2 ~ODOl vmers 3 Ideal catalyst systems for the productlon of block copolymers 4 are s~ngle-slted livlng catalysts. L~v~ng catalysts are those ;ystems r 5 1n ~hlch cha~n trans~er 1s nonex~stent and the rate of ln~t~at~on ls 6 fast compared to propa~atlon. Cat~lyst3 ~hlch have f1n1te chaln 7 transfer rates may also be useful for the productlon of block and 8 tapered copolymers ~f the rate of propagat'on 1s fast relat~ve to g termination. It ~s also ~mportant that the aver3se chaln l~fet~mes I0 are reasonably long (~lnutes to hours) in order to perm~t adequate 11 time for modlf~cat10ns o~ the reactor condltlons te.g. chang1ng 1~ monomer feed streams). ~hile most reasonably stable lon~c catalysts 13 descr1bed above ~ill under su~table cond~t~ons produce block and/or 14 tapered copolymers of nonpolar olefins, lt ~s preferred that the 15 catalyst be: l) thermally stab'e ~recoverable as a s~ngle 6 organometallic complex~, 2) versatile ln terms of random copolymer 17 synthes1s t~.e. cap~ble of prepar~ng HDPE, l-PP, s-PP, EP-rubber, 18 LLDPE etc.), 3) capable of produc'ng high mole'ul~r ~e'ght polymers at 19 reasonable temperatures and pressures, 4) hlgh act~v~ty ~fast 2~ propagat~on catalysts) and 5) ilov in cha~n ter~inat~on reactlons so ~l that fe~ tha'ns of polymer product are produced per hour per slte.
22 Ionlc ~atalysts of the for~ ~A-CpMMe(L')JtB~C~F~)~tX~)~ are 23 the prefcrred catalysts for the productlon of block and tapered 24 copolymers of ethylene, l-olefins, d'enes, cycl k olef1ns and other 25 unsaturated monomers. Ion~c catalysts of thls form ~here H Hf are 26 the most preferred catalyst systems because they are more stable, 27 produce higher molecular ~e~ght copolymers, and have longer chaln 28 llfetlmes than correspond~n9 2r or Ti-based systems. Polymer~zations 29 using hafnlum systems of th's form under standard random copolymer 30 condit~ons as descr~bed ~n our copend~ng U.S. Patent Application No.
31 )33,480 produce high molecular ~e~ght HDP, LLDPE, a-PP, ~-PP, s-PP, 32 and P-rubber at rates comparable to s~m~lar 2r-based catalysts.
33 Tapered and block copolymers conta~nlng these segments can be 34 produced using the approprlate hafn~um )on~c catalyst us~ng the 35 technlques and process cond~tions set forth ~n the follo~1ng sections.

~ . . .
., , . . .
.

, , .. . ~. .

WO 91/lZ28:~ PCI'/lJS91/00835 .

~d ~. .t 5~35 -- 26 --1 Processes FQr the Product~on of Block and ~aeered Copolvmers 2 Many procedure~ for modlfy~ng the reactor condltlons and 3 monomer feeds for the product~on of block copolymers have been 4 developed and appl1ed us1ng conYentlonal Z1egler-Natta catalysts.
The patent ltterature concernlng block copolymer from Z~egler-Natta 6 ca~alysts d~sclose a varlety of processes for alterlng reactor 7 cond1tions. The proresses lnclude batch reactors and sequent1al 8 add1tions techn~ques, ser1es batch reactors, loop and tubular 9 reactors, and fluld12ed bed reactors. A revie~ of the processes and lO patents 1s g1~en 1n chapter 4 of Block CopolymersU ~D. C. ~llport ll and ~. H. James; John ~ley and Ssns, Ne~ York 1973~. As 1nd~cated 12 supra, the appt k at10n of these processes us~ng conventlonal 13 catalysts in general produces broad molecular ~e~ght d~str~butions of 14 poorly def~ned polymer blends. In pr~nclple, the catalysts of thls lS ~n~ention can be used in any of the processes descrlbed above for the 16 product~on ~ell-def~ned block copolymers of h19her pur1ty than 17 obta~ned us~ng conventlonal 21egler-Natta catalysts.
18 The most demanding process, that ~s the process ~hich 19 re~u~res the longest chaln l~fetimes, ls the sequentlal addlt10n.
20 ~hen the catalyst or 1nit~ator produces grovlng chains ~ith 21 suff1c~ently long 11fet~mes, the sequent1al addition techn~que altows 22 for the production of block copolymers hav~ng non-tapered trans~t~ons 23 bet~een different polymer segments. Sequent~al addit10n techn~ues 24 are commonly used to produce styrenic bloek copolymers ~Kraton for 25 example) using an10n~c 1n1tiators.
26 In the f~rst step of the sequent1al add1tlon process 27 employed 1n accordance ~1th th1s lnventlon the catalyst ls placed ln 28 a ~ell st~rred batch r-eactor in a sultable solvent and flrst segment 29 of the block eopolymer ls gro~n by add1ng a spec1fic number of molar 30 equ1valents of ~lonomer(s). The catalyst consumes all of the 31 monomer(s) pr10r to add~t10n sf the second monomer~s) (a d~ffQrent 32 set of ~onomers than ~n the first step). This procedure can be -33 repeated to prepare multibloek copolymers.
Sequeni:1al Add~tlon Condlt~çn~
34 For a g1Yen catalyst and target block or tapered copolymer a ... .. . .

WO 91/122~5 P~/U~i91~00835 --- 2~ ?~ .

1 solvent temperature and catalyst concentratlon must be chosen so 2 that 1) narro~ molecular ~e~ght d~strlbution hlgh molecular ~e~ght 3 copolymer segments can be syntheslzed; and 2) the molecular ~e~ght of 4 the copolymer segments can be controlled by varylng the catalyst-to-monomer molar ratlo. Under these condltlons the system 6 15 behav~ng ln a quaslllvlng fash~on (l.e. slo~ chaln transfer) and 7 narro~ ~olecular ~elght block copolymers can be prepared ln h~gh 8 y~eld. Hethods for choos~ng the cond~tlons for a part~cular catalyst 9 system are s~ven below.
~$olvent Preferably the solvent should normally dlsperse or d~ssolve 11 the catalyst to form a Hell-m~xed system. ~he most preferred 12 catalysts for block copo1ymer synthesls 13 ~ACpHfMe(L )]EB(C Fs)~ are prepared ln toluene and form non-m~slble 14 toluene-disPersible phases. Thls two-component phase conta~ns the 15 catalyst and a part~cular amount of toluene; the concentrat~on of 16 toluene ~n the catalyst phase depends on temperature and the structure 17 of the catalyst. Addit~on of an al~phatic 1~ hydrocarbon to the toluene-catalYst emuls~on causes lmmed~ate 19 prec~p~tat~on of the eatalyst from solut~on to g~ve a soft ~axy 20 non-disperslble catalyst deposlt. Wh~le allphatlc hydrocarbons 21 fluorinated hydrocarbons and chlorlnated aromat~c hydrocarbons may 22 be used ln th~s 1nventlon the preferred solvents for the preparat~on ~3 of block copolymers from the most preferred catalysts are aromat~c 24 hydrocarbons ~uch as toluene xylene ethyl benzene and the llke.
25 The lack c~ solub~lity or co~pat~b~l1ty of the catalyst phase ln the 26 aromatlc solvent does not present s~gnlflcant problems ln terms of 27 molecular ~e~ght broaden~ny because the phase ls h~ghly d~spers~ble 28 even at lo~er temperatures.
TemDera.ture 29 The reactor temperatur2`strongly affects the yleld of block 30 copolymer and must be ad~usted dependlng on the type and 31 concentrat10n of monomers and catalyst used. The general procedure 32 for determ~nlng thls cond~t~on ls to 1) flnd the maxlmum temperature 33 ~here hlgh molecular ~e~ght polymer segmenti can be prepared and 2) . .
.. . . - . .
. ~ ~ . , -- . .. .. . - .
... .. . . ..

"' ' . . '. . '' ' . :: , ;,',,-, . '',;, , , '' . '' .; '' . .

WO 91/1~8~ P~/US91/00835 , .
Z~ S~35 1 conf~rm the molecular welght is controlled by the catalyst-to-monomer 2 ratio at thls temperature. The general trend 1s that hlgher 3 temperatures cause cha~n transfer to be more rap~d relatlYe to 4 propagat~on and therefore 91ve lo~er block copolymer y~elds. The process may be carried out at temperatures of -80-C to 80-C, ho~eYer, 6 lt is preferred that the temperature be ~n the range of -lO-C to 7 20-C.
~ oncentrat~on of ~atalYst 8 The concentrat~on should be h~gh enough to produce 9 s1gnific~nt rates of polymer~zat10n under the generally loY pressure IO cond~t10ns of sequential add1t~on. ~he concentration should not be 11 so h~gh as to produce uncontr~llable exotherms upon exposure to the 12 monomer. The exotherm can be controlled, ho~ever, by ad~ust1ng the 13 rate of monomer addition durlng the formation of a block segment.
l4 This le~el of control allo~s for a large range of acceptable 15 catalysts concentrations. The process may be carr~ed out at catalyst 16 concentrat~ons rang1ng from about 6 x lO to about 6 x lO~l 17 moles of catalyst/11ter of solutlon, hoYever it 1s preferred that 18 catalyst levels be in the range of l x l9~~ to about 3 x 10~
I9 moles of catalyst/11ter of solut10n.
Monomer Concentrat~on The amount of monomer added depends on the molecular ~elght 21 of the targeted polymer and the moles of act~ve eatalyst in the 22 reactor. Molar rat10s of monomer to catalyst may be 1n the range of 23 about 10:1 to about 10,000~ he monomers may be added qu kkly or 24 may be metered ln to the reactor to control exotherms.
Order of_Monomer Add~t~on Prec~p~tat10n of polymer ~th catalyst attached) causes 26 undes~rable broadenlng of the molecular ~elght d~stribution due to 27 mass transport limltat10ns and poor m~x1ng. It ~s therefore 2~ prefe~red to prepare the soluble block (generally the elastomer1c 29 segment) ~n the flrst stage of the react10n. Thus, as lndicated 1n the examples, ~hen ethylene 1s added 1n the f1rst step ~n ~he 31 synthes1s of a HDPE-b-atact~c-PP diblock copolymer the ln1t~ally 32 formed polyethylene prec1p1tates with th~ catalyst and the f1nal - . :,. . . : : - , i . . .
:,: ` ` ,' , ' . ' . ,:
.~

2~ ~ !75 1 ~olecular ~e19ht d~str~butlon of crude block copolymer product ls 2 rather broad (~/Mn 3.0). Add~tlon of propylene in the flrst step 3 produces a system ~hlch rema1ns homogeneous throughout the block 4 copolymer synthesls, y~eldlng a crude product hav~ng a much narro~er ~w~n O (1.7 - 1.8).
Presarat~on of TaDered and Random CoDolyer~
6 Add~tion of sto~chlometr k amounts of a ~lxture of t~o 7 oleflns to the reactor under block copolymer condltlons ~
8 naturally produce tapered copolymer because the monomers ~111 9 generally have dlfferent react~vltles ~'th the ~atalyst. Thus, the 10 head of the polymer ~lll be r1ch ~n the more react~ve comonomer ~hlle 11 the polymer tall ~lll contaln larger amounts of the slo~er react~ng 12 ~omonomer. The extent of taper~ng ~lll depend on magnltude of the 13 d~fference of monomer reactlvlty. The extent of tapering can be 14 controlled by meter~ng the two monomers 1nto the reactor at dlfferent 15 rates.
16 Random copotymers such as non-crystalline ethylene-propylene 17 rubber can be made under block copolymer conditions by adding the 18 fast monomer ~ethylene) to the catalyst/propylene mlxture at a rate 19 ~here the deslred amount of ethylene has been added ~hen al1 the 20 propylene has been consumed. This procedure 1s e~empl~fled for a 21 ethylene-propylene elastomer conta~n~ng 50 ~ole % propylene.
810ck ~o~olymer Products 22 The novel polymer products of thls lnvent~on are olefin~c 23 block and tapered copolymers hav~ng narro~ molecular ~e~ght 24 distr~butions and ~ell def~ned dl-, trl-, multlblock or tapered structures. The polymer segments ~hlch can be 1ncorporated ~nto 26 these arch1tectures 1nclude l) elastomers such as atact~c 27 polypropylene, atact1c poly-l-oleflns, and ethylene/l-olefln 28 copolymers ~hereln the ethylene comonomer 1s a Ca-C~
29 a-olef1n such as ethylene-propylene, ethylenQ butene, and ethylene-octene copolymers ethylene-propylene-dlene terpolymers and 31 other crossllrkable elastomerlc oleflns; 2) thermoplastlcs suth as 32 h~gh denslty polyethylene, llnear lo~ dens1ty potyethylene having 33 meltlng polntsi from 80-135-C (e.g. ethylene-propylene and other .. .. . .

, ~ .

: : ., .
. ~ , .. . . .

WO 91~1228S PCI/US91/00835 ,~ ..

~ "_ 1 ethylene-l-olef~n copo~ymers ~hereln each l-olefln has from about 4 2 to 20 carbon atoms), ethylene/d1ene copolymers such as 3 ethylene~ethyldlene-norbornene copolymers, 1sotactic polypropylene 4 hav1ng melt~ng po~nts from lOO-C-165-C, syndlotaetle polypropylenes haY1ng melt~ng polnts from 100-C-165 C" heml-~sotact~c polypropylenes 6 and other crysta11~ne l-olef~n homo and copolymers, and 3) glasses 7 suoh as homo-polycyclopentene, homopolynorbornene and the llke. The 8 average molecular ~elght of the polymer segments ~ncluded ln the 9 nove1 block copolymers of th~s tnventlon can be ln the range of from 100-1,000,000 daltons, preferably from 30,000 to 200,000 daltons.
11 The molecular ~eSght d~strlbut1Ons SM~/Mn) of the crude and/or 12 fract~onated block copolymer are 1n the range from about 1.0 to about 13 5 o, preferable from about 1.1 to about 2Ø As lnd~cated above and 14 ~n the examples follo~ing the percentage of block eopolymer ln the crude product can vary from about 1~ to lOOX, preferably from about 16 50% to about 90X depending on the appl~cation and the cond~tions of 17 the eXperiment 18 The block copol~ners of this invention can be represented by 19 the follo~ng general formulae:

2Q (A~)(A2)tA~) (An) 21 ~here~n each A ~s 3 poly~er segment having an average molecular 22 weight from about 100 to about 1,000,000 daltons chosen 1ndependently 23 from homopol~ners conslstlng of HDPE~ homo and copolymers of cycl1e 24 olef1ns, such as polyeyelopentene and polynorbornene, and lsotactic, atact~c, and synd~otact1c poly-l-oleflns such as atactlc PP~
26 1sotact1c-PP, synd1~tactlc-PP; random copolymers of l-oleflns and 27 d1O1ef~ns such as ethylene-propylene rubber, 28 ethylene-propylene-hexad1ene rubber, ethylene-butene rubber, llnear 29 lo~ dens1ty polyethylenes, such that no ad~acent segments ~re the sa~e polymer colnposlt~on.
31 Novel block copolymers of th1s 1nvent1On 1nelude but are not 32 11m1ted to dlblock copolymers such as tHDPE)(EP), t~-PP(EP), 33 (LLDPE)(a-PP), (HDPE)(a-PP), ~LLDPESHDPE) and the 11ke, and tr1bloc~

PCI`/US91/00835 ~2 ~ ~ 5 1 copolymers such as (HDPE)(EP)~HDPE), (HDPE)(a-PP)(~DPF), 2 (HDPE)(EP)LLDPE), (LLDPE)(a-PP)(LLDPE), (HDPE)(a-PP)(LLDPE), 3 (i-PP)(EP)(i-PP), (s-PP)(EP)(s-PP) and the like. It will be recognized 4 to those well versed in the field that the isotactic polypropylene segments contained in the block copolymers of this invention have 6 microstructure de~ects which are not observed in conventional i-PP
7 materials prepared using titanium Ziegler-Natta catalyst. The 8 microstructure defects which are unique to isotactic polypropylenes 9 prepared using metallocene catalysts arise from 1-3 and 2-1 additions to 10 propylene. The melting points o~ such materials can vary from 60C to 11 165C depending on the totAl number total defects.
12 The tapered copolymers can be represented by s1mllar general 13 formula where the transltlons bet~een ldDalized polymer segments A
14 are gradual. These gradlent transltions bet~een segments are 15 represented by arro~s.

16 tA )---~(A2)~ (A,)-__~ (An)~

17 An example of thls ~ould be a po)ymer prepared by reacting a 50-50 18 mlxture of ethylene and pro~ylene Y1th a 11v~ng catalyst ~hlch has a l9hlgh preference for ethylene over propylene. The tapered polymer 200bta1ned ~n such an experlment Yould be designated by the follo~iny 21 formula:

22 HDPE--->EP--->a-PP

- .. - . .. , ; .. . . .

WO 91/1~28~ PCI/US91/00835 25;f~J~3~

EXAMPlES

1 CatalYst PreParation. The catalyst used in the following examples 2 was prepared in dry, deoxygenated toluene (5.0 cc) by reacting 3 Cp2HFMe2 with one equi~alent of 1DMAH~lB(F~fp)4~ (where DMAH -4 PhMe2NH+ and pfp ~ C6Fs) at room temperatur for 5-10 minutes. The reaction is known to cleanly produce methane gas and a single 6 ionic catalyst ICp2HfMe(PhNMe23]~B(pfp~4].

ExamDle I
First Ethvlene then Propylene.
7 The reactor was cooled to 0C and charged with 400 mls of 8 toluene and 0.30 mmoles of catalyst. Ethylene (4.0 grams; 0.143 9 moles) was added to the reactor. After all the ethylene was consumed, propylene (S grams; 0.139 moles) was added; after 30 11 minutes the reactor was dropped and the product collected. ~he 12 crude product contained S0 mole X propylene, had an 13 Hn ~ 87,000 with a molecular weight distribution of 3Ø The 14 crude product was washed with hexane at room temperature to remove any -PP which was-not in the form of block copolymer. The hexane 16 insoluble material contained cyrstalline HDPE (as determined by 17 IR) and 30 mole % propylene; the Mn was 144,000 with a molecular 18 weight distribution of 1.89. ~he hexane soluble fraction was 19 PP, did not contain ethylene (by lR), and had an Mn Of 63,000 with a molecular weight distribution of 1.47. Based on the extraction 21 studies, it was concluded that 50-60% of the -PP chains were 22 incorporated into a block coplymer under these conditions~

.. ... .

.: , . , ; ., j , ,.,. : ;

; ,: ,, : : . ;~ , ~ . .. . :: . ,. . .-, . , : , :

WO 91~1228~ PCI/US91/00835 25~ 25 I Mn - 87 000 ~th a molecular ~e'ght dlstrlt)ution of 3Ø The crude 2 product ~as ~ashed ~th hexane at room teml~erature to remove any 3 a-PP Yh~ch was not ~n the form of block copolymer. ~he hexane 4 ~nsoluble mater1al contalned crystall~ne HDPE (as determlned by IR) and 3~ mole ~ propylene; the Mn ~as 144 00t) ~lth a molecular ~e~ght 6 d~strlbutlon of 1.89. The hexane soluble fract1On ~as a-PP, d~d 7 not contain ethylene (by IR) and had a Hn of 63 000 ~th a 8 molecular Yeight distr~bution of 1.47. Based on the extract~on g studles 1t ~as concluded that 50-60X of the ~-PP cha~ns ~ere Io lncorporated lnto a block copolymer under these cond~tlons.

Fxample 2 Flrst Propvlene Then Ethy!_ne lI The procedure of Example l as repeated except propylene was 12 added first. The crude product had 41 mole X propylene (IR) a Hn 13 o~ 170 000 ~ith a molecular we~ght distrlbution of 1.78. A pad Yas 14 pressed and extracted ~1th hexane for 4 hours. At th~s po~nt the m~terial contained 37 mole X propylene and very crystall~ne HDPE.
16 The pad ~as further extracted ~th toluene at room temperature for 50 17 hours ~ith no loss of ~eight. The extracted ndiblock had a Hn f 18 230 000 and a molecular ~e~ght distribution of 1.48 (the hexane lg solubles ~ere a-PP hav1ng a Mn of 125 000 and a molecular ~eight 20 d~stribution of 1.72).

Example 3 Molecular Weight ~ontrol In Block Copolvmer Svn~hesls 21 Us1ng the procedure ln Example 2 3.0 grams of propylene 22 (0.070 moles) ~ere added to 0.30 mmole of the hafnlum catalyst.
23 After the propylene (0.071 moles) ~as completely consumed 2.0 grams 24 Of ethylene ~ere added to the system. ~he result1ng product Yas 25 ~ashed ~1th hexane at room temperature to remove any a-PP. The 26 result1ng block copolymer had a Mn of 107 000 and a molecular ~e~ght 27 d~stribut1On of 1.68 and conta1ned 42 mole ~ propylene by IR
28 speceroscopy~

, . , . , . ; :~ , .: ..

WO 91/12285 PC~/US91/0083~
!~ -2~-~5~!35 Exam~le 4 Effe~t of Temperature 1If the temperature ls ralsed the effect ls to lo~er the 2 eff~clency of the block formatlon. The temperature ~as ralsed from 3 O-C to lO~C and the block~ng efficiency ~as reduced to less than lOX
4 to 65~. ~hen the temperature ~as lo~ered to -5~C the block1ng efficlency lmproved 78X.

ExamDle S
The Effect of Increas1ng the T~me Between the A~dltlon of Monomers 6A ser~es of block copolymer12at10ns ~ere run at O-C and the 7 t~me bet~een the add~t~on of propylene and ethylene ~as varled from 6 8 to 42 mlnutes. The crude products ~ere collected analyzed by GPC
9 and IR then extracted ~lth hexane at room temperature for 65 hours 10 to remove unblocked ~-PP. In a ~ell-behaved system ~here~n the ~-ll extractlon technlque removes all of the ~-PP a logr~thmlcally -~
12 increase ~n the percent of hexane extractables vith time would be 13 expected. The data of thls example ls sho~n ln Fig. l tn graph~cal 14 form. The Y-axls represents the percent of polypropy)ene ~h~ch ls lncorporated lnto the block copolymer. The extrattables ~ere 16 ~solated and analyzed by GPC and IR; they ~ere all pure 3-PP. . The 17 correlat~on ls close to the llnear result expected so that thls 18 techn~que can be used to e~aluate the kinet~cs of cha~n loss under a 19 var1ety of conditlons. Thls result conf~rms the ab11ity to make true bloc~ copolymers and confirms that hexane extractlon 1s a good 21 measure o~ block copolymer efflc~ency for this polymer system.

.; . . , . , , .,. ., . ., ~ . . , , . ., , .. , , _ , .... . . . ..
" ", ... .....

w o 91/~2285~CT/VS91/0~835 2 ~ J`~3;~

~xamDle 6 Preparat~on of EP
1In ~h~s example, 1.6 grams of propylene ~0.037 moles) ~ere 2 added to ~Cp2HfMe(L)]IB(pf~)4~ (0.30 mmole) 1n 400 cc of 3 toluene at O-C. Immed~ately after the propylene add~tlon, 1.1 grams 4 of ethylene (0.039 ~oles) ~as metered 1n over 3 m~nutes. After s~x m~nutes, the çroduct was recovered y~eldlng 2.7 grams of amorphous EP
6 rub~er. The product ~as non-crystall~ne by IR; the polymer had a 7 Mn of 96,000 and a molecular ve~ght distr~but~on of 1.69.

Exam~le 7 Prepar~tlon of EP
8 In th~s example, 3.2 grams of propylene (0.074 moles) ~as 9 added to tCp2HfMe(L)J~B(pfp)~ (0.30 ~mole) ~n 400 cc of 10 toluene at O-C. Ethylene (2.2 grams; 0.078 mo~es) was added to the 11 reactor oYer 5.5 minutes. The product ~as recovered y~eld~ng 5.7 12 grams of EP rubber havlng a Mn of 155,000, and a molecular weight 13 d~stribution of 1.48. The IR sho~ed some degree of PE-crystallinity.

ExamDle 8 PreDarat~on of ~P-b-HDP~
14 Example 6 ~as repeated to prepare ~l~v~ns~ P-rubber. After all the xnomer had been consumed, ethylene (1.1 grams) ~as added to 1~ prepare the des~red block copolymer. The product ~as recovered 17 y1eld~ng 4.25 grams of copolymer. The IR shoYed PE crystall~n~ty and 18 the polymer had thermoplast1c-llke propertles. The onset of Tg ~as 19 -52.9-C and the product had a melt~ng point of ll9~C. ~he Mn f 2~ the crude product ~as 161,000 b~th a ~olecular ~e~ght distributlon of 21 1.59-- . : ............... . ..... ; ,. .. ,. :, : . ~ .. - -.. . .. ; ..

W O 91/1228~ PCT/US91/00835 ~; s~iQ?~
- 3fi -1 ~xa~ple 9. The intention of this example is to demonstrate 2 that slow chain transfer can be used to catalytically prepare 3 block copolymers. This is an example of in-situ catalyst 4 recycle leading to the production of mixtures of small amounts of homopolymer and mixtures oE multiblock copolymers 6 ~AB, ABA, BAB etc).
7 The reactor was cooled to OC and charged with 400 mls of 8 toluene and O.lS mmole of catalyst. In step 1, propylene 9 ~1.5 grams) was added to the well stirred reactor causing a 11 pressure increase of 7 psi. After 7 minutes the pressure in 12 the reactor dropped to zero and the reactor was vented 13 through a nujol bubbler to remove any residual propylene in 14 the system. In step 2, ethylene (1.0 grams) waS added. The ethylene was consumed in less than one minute. After all the 16 ethylene was consumed the reactor was vented. These 17 sequential steps were repeated S more times resulting in 18 similar monomer conversion rates. The reactor was dropped 19 and tbe the product was collected yielding lS grams after drying. The crude product was analyzed by GPC and had a ~n =
21 122K and a MWD = 2.2. The melting point waS 126C by DSC and 22 the IR indicated the presence of high crystallinity 23 polyethylene. A thin pad weighing 1.25 grams was corpression 24 molded and extracted with hexane a room temperature for 72 ~ours at room temperature. ~he pad ~as removed, dried and 26 wei~hed yielding 1.13 grams of insoluble material. She 27 insoluble material was analyzed by GPC and DSC and had a Mn =
2~ 171X, a MWD = 1.8 and a melting point of 126C. The soluble 29 material was isolaeed ~0.12 qrams) and ~as identified as atactic PP. The extraction data indicated that 8~ of the 31 polypropylene is bonded to insoluble polyethylene segments.
3~ The data are not suf f icient to detect homo-polyethylene, or 33 to quantify the ratios of the varlous possible multiblock 34 copolymers. ~he observation, however, that the Mn of the crude and extracted products in this experiment are only 36 slightly higher than is typical of a standard A-B sequential 37 addition ~Mn = 1201-140K) at the same monomer:catalyst ratio 39 suggests that the chain lifetimes are not sufficiently long to produce high amounts of triblock or other higher order 41 block copolymers.

.: : ...... -'".... ' i':

W O 91~1228~ PCT/US91/00~35 . . 2~t~J11~5 I Eyamp~e 10. The reactor was cooled to OC an~ charged with 2 400 mls of toluene and 0.15 mmole of catalyst. In step 1, 3 propylene (1.5 grams) was added to the well stirred reactor 4 causing a pressure increase of 7 psi. After 7 minutes the pressure in the reactor dropped to zero and the reactor was 6 vented through a nujol bubbler to remove any residual 7 propylene in the system. ln step 2, ethylene (1.0 grams) was 8 added. The ethylene was consumed in less than one minute.
9 After all the ethylene was consumed the reactor was vented and in step 3 propylene ~1.5 qrams) was added. The propylene was consumed in 7 minutes and after an addition 20 minute 12 ~aiting period steps 1,2 and 3 were repeated. The reactor 13 was dropped and 4 grams of crude dry product was isolated.
14 The crude product was analyzed by GPC and had a Mn = 140K and a MWD = 1.1. The I~ spectrum indicated the presence of high 16 crystallinity polyethylene. A thin pad weighing 1.07 grams 17 was compre~sion molded and extracted with hexane a roo~.
18 temperature for ~2 hours at room eemperature. The pad was 19 removed, dried and weighed yielding 0.87 grams of insoluble material. The insoluble material was analyzed by GPC had a 21 Mn = 192K, a ~.~D = 1.4. The soluble material was isolated 22 ~0.20 grams) and ~as identi~ied as atactic PP by I~ and ~M~
23 spectroscopy. The extraction data indicated tha~ 81~ of the 24 polypropylene is bonded to insoluble polyethylene segments.
~ample 11_ In this example we describe an attempt to 26 prepare an ~BA triblock copolymer where the A-block ~s high 27 density polyethylene and the ~-block is elastomeric atactic 28 polypropylene. We disclose a technique where a small amount 29 of propylene (5~ o~ the amount added in the B-step) is added in a prepolymerization step. The effect of this is to 31 solubilize the insoluble polyethylene A-segment and prevent 32 precipitation of ~he living polymer. When this procedure is 33 used a clear, apparently homogeneous reaction mixture is 34 formed. Similar experiments where the prepolymerization step is not used gives a heterogeneous reaction mixture, lower 36 blocking efficiencies and broader molecular weight 37 distributions.

.... . . .. . .......... .

:: . , " , ~ . , :, . ~:, . : ; , . - '::. :

- :'': -:" :'. ':' ' , . . ' ' ~ 1 : ,. , , . . , :,, . .;. ~ :: . . . ::' : .' . -.:.:: : :: :: ., :;

W O 91/12~8~ PCT/US91/00835 2~ ~ 5 1 The reactor was cooled to OC and charged with 400 mls of 2 toluene and 0.15 mmole of catalyst. In a prepolymerization 3 step 1, propylene ~0.15 grams) was added to the well stirred 4 reactor. After 7 minutes the pressure in the reactor dropped to zero and the reaCtOr was vented through a nujol bubbler to 6 remove any residual propylene in the system. In step 2, 7 ethylene (0.5 grams~ was added. After 2 minutes, propylene 8 t3.0 9rams) was added to the well stirred reactor causing a 9 pressure increase of 7 psi. The propylene waS consumed in 4 minutes a uhich point the reactor ~as vented and ethylene 11 (0.5 gra¢s) was added. The reactor was dropped and 1~ approximately 4 grams of crude dry product waS isolated. The 13 crude product was analyzed by GPC and DSC and had a melting 14 point of 122C, a Mn - 173X and a MWD 3 1.9 (with a bimodal shape). A thin pad ~eighing 1.295 grams was compression 16 molded and extracted with hexane a room temperature for 72 17 ~ours at room temperature. The pad ~as removed, dried and 18 ueighed yielding 1.17 grams of insoluble ma~erial. The 19 resulting material has thermoplastic elastomeric properties.
The extraction data indicated that 86~ of the polypropylene 21 is bonded ~o insoluble polyethylene segments.
22 ~xamole'2 The reactor was cooled to OC and charged ~ith 23 400 mls of toluene and 0.15 mmole of catalyst. In a 24 prepolymeri~ation step 1, propylene (0.15 grams) was added to the well stirred reactor. After 7 minutes the pressure in 26 the reactor dropped to zero and the reactor was vented 27 through a nujol bubbler to remove any residual propylene in 2~ the system. In step 2, ethylene (0.25 grams) was added.
29 After 2 minutes, propylene ~3.0 grams~ was added to the well stirred reactor causing a pressure increase o~ 7 psi. The 31 propylene ~as consumed in 4 ~inutes a~ which point the 32 reactor ~as vented and ethylene (0.25 grams) was added. The 33 reaceor was dropped and approximately 3.5 grams of crude dry 34 product was isolated. The crude product was analyzed by GPC
and DSC and nad a melting point of 122C, a M~ = 160K and a 36 MWD = 1.8 (with ~ bimodal shap~). A thin pad weighing 1.2B8 37 grams was compression molded and ex~racted with hexane a room 38 temperature for 72 ~ours at room temperat~re. The extremely 39 swollen pad was removed, dried and weighed yielding 1.165 grams of insoluble ma~erial. The resulting material has 41 thermoplastic elastomeric properties. The extraction data 42 indicated that 88~ of the polypropylene i~ bonded to 43 insoluble polyetllylene segmentS. The insoluble product was 44 analyzed by GPC and had a Mn ~ 184K and a MWD = 1.6 (with a bimodal shape).

- : , ,: : ~ . ., , - . . ..
:, . ::: " , :::, , .: :

:.-. : - : ~: ., : :. .: - . ,: , :.:
:, - ,. : ~ ~,,, ~. , .. , , ' ,; . ::
,: : :,.,: .. :;

Claims (15)

- 39 -

1. A process for the production of block copolymers comprising:
(i) contacting a first olefinic monomer(s) with a catalyst which is the reaction product of:
(a) a metallocene component, and (b) a second component having a cation capable of donating a proton and a compatible non-coordinating anion to produce a first living polymer; and (ii) sequentially adding to said living polymer at least a second monomer(s) to copolymerize with said first polymer to produce a multi block copolymer; and (iii) recovering a block copolymer

2. The process of claim 1 wherein the block copolymer is a diblock copolymer.

3. The process of claim 1 wherein the block copolymer is a triblock.

4. The process of claim 1 wherein the catalyst reaction product is of the formulae:
[A-CpMX1][C2B9H11)2Co]
[A-CpMX1(L')][B(C6F8)3(X3)]
[(A-CpMX1)2X1][B']
wherein: M is titanium, zirconium or hafnium; (A-Cp) is either (Cp)(Cp*) or Cp-A'-Cp* and Cp and Cp* are the same or different substituted or unsubstituted cyclopentadienyl radicals; A' is a covalent bridging group containing a Group IV-A element; L' is a neutral Lewis base; X1 is a hydride radical, hydrocarbyl radical having from 1 to about 20 carbon atoms, substituted-hydrocarbyl radical, wherein 1 or more of the hydrogen atoms are replaced with a halogen atom, having from 1 to about 20 carbon atoms, or organo-metalloid radical comprising a Group IV-A element wherein each of the hydrocarbyl substituents contained in the organo portion of said organo-metalloid, independently, contain from 1 to about 20 carbon atoms; C1-C20 and X3 is a hydride, halide, hydrocarbyl radical, a C1-C20 hydrocarbyl radical wherein one or more of the hydrogen atoms is replaced by a halogen atom, organometalloid radical wherein each hydrocarbyl substitution in the organo portion contains from 1 to 20 carbon atoms and the metal is a Group IVA metal.

5. The process of claim 4 wherein the catalyst reaction product is represented by the formula:
[A-CpMX1(L')][B(C6F5)3(X3)]

6. The process claim 1, wherein the catalyst is the reaction product bis(cyclopentadienyl) hafnium dimethyl and N,N-dimethylanilinium tetrakis(pentafluorophenyl)boron.

7. The process of claim 1 wherein said steps of reacting, copolymerizing, introducing and repeating are carried out at a temperature of from about -5°C to about 10°C.

8. The process of claim 1 wherein any of said monomers is selected from ethylene, propylene, 1-butene.

9. Olefinic block copolymers having a Mw/Mn of from about 1 to 5 represented by the formula:

(A1)(A2)(A3)?????(An) wherein each A represent a polymer segment having an average of Mw of from 100 to about 1,000,000 daltons, each adjacent A represents a different olefinic polymer segment, A being selected from HDPE, atactic-1-olefins, isotactic 1-olefins, syndiotactic 1-olefins, homo-and copolymers of cyclic olefins, and random copolymers of 1-olefins and diolefins.

10. The olefin block copolymers of claim 9 wherein the polymer segments are selected from are atactic-polypropylene, isotactic-polypropylene and syndiotactic-polypropylene.

11. Olefin block copolymers of claim 11 wherein said block copolymers is a diblock.

12. Olefin block copolymers of claim 11 selected from (HDPE)(EP), (i-PP)(EP), (LLDPE)(a-PP), (LLDPE)(HDPE).

13. Olefin block copolymers of claim 10 wherein said block copolymer is a triblock.

14. Olefin block copolymers of claim 13 selected from (HDPE)(EP)(HDPE), (HDPE)(EP)(LLDPE), (LLDPE)(a-PP)(LLDPE)(HDPE)(a-pp)(LLDPE), (i-PP)(EP)(i-PP)(s-pp)(EP)(s-PP).

15. Mixtures of homopolyolefins, and di- and triblock copolymers, said block copolymers produced by the process of claims 2 and 3.